Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
  • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
  • C07C331/02—Thiocyanates
  • C07C331/04—Thiocyanates having sulfur atoms of thiocyanate groups bound to acyclic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C333/14—Dithiocarbamic acids; Derivatives thereof
  • C07C333/18—Esters of dithiocarbamic acids
  • C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
  • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D277/36—Sulfur atoms

Definitions

• the present invention relates to a process for the preparation of halogenated 2- (3-butenylsulfanyl) -1, 3-thiazoles of the formula (I),
• R stands for H or F.
• Dithiocarbamic acid in particular the ammonium dithiocarbamate with an aqueous solution of chloroacetaldehyde under acidic or neutral conditions.
• the object of the present invention was therefore to develop a process which is an alternative to the processes mentioned and which, bypassing the intermediate 2-mercapto-1,3-thiazole, leads directly to the desired end products of the formula (I).
• R is H or F and preferably F
• X represents bromine, chlorine, mesylate or tosylate and preferably bromine
• M + represents hydrogen, an ammonium ion, a tetraalkylammonium ion or an alkali metal ion, for example K + or Na + ,
• 3,4,4-trifluoro-3-butenyl-1-dithiocarbamate of the formula (V) can be very easily, for example, either with acetaldehyde, chloroacetaldehyde or its acetals to give 2 - [(3,4,4-trifluoro-3-butenyl) sulfanyl] - 1,3-thiazole without fear of decomposition and release of dangerous CS 2 and without resinous by-products such as occur in the reaction of ammonium dithiocarbamate
• Chloroacetaldehyde occur. Such by-products are also mentioned in EP 0 926 140 AI.
• the oxidation-sensitive 2-mercapto-1,3-thiazole used in the previous processes can be dispensed with.
• an acid e.g. HC1, p-toluenesulfonic acid or methanesulfonic acid are important.
• the method steps according to the invention can each follow one another directly or can also be carried out individually, the respective product also being able to be cleaned.
• the compounds used in process (a) according to the invention for the preparation of the compounds of the formula (IV) are characterized by the formula (H).
• X particularly preferably represents bromine and R particularly preferably represents fluorine.
• the compounds of formula (II) are known compounds.
• Compounds of formula (II) in which X represents F are e.g. described in WO 86/07590 and can be prepared by the process specified there.
• M + preferably represents potassium, sodium or ammonium ions, particularly preferably ammonium ions.
• rhodanide salts (thiocyanates) of the formula (LU) such as, for example, ammonium rhodanide (NH 4 SCN) are known compounds and are commercially available.
• R preferably represents hydrogen or fluorine, particularly preferably fluorine.
• the compounds of the formula (IV) can be prepared by process (a) mentioned above.
• the production of trifluorobutenyl dithiocarbamates has been e.g. in US 3,510,503, where the reaction of a 4-bromo-l, l, 2-trifluoro-l-butene takes place, inter alia, with a substituted ammonium dithiocarbamate or, after condensation, a suitable one
• the compounds used further in process (b) according to the invention for the preparation of the compounds of the formula (V) are hydrogen sulfide (H 2 S) and its salts. These compounds can be described generally with the formulas MSH and M 2 S, where M + stands for example for ammonium ions or sodium ions. H2S, ammonium sulfide, NaSH solution or Na 2 S are preferably used in process (b) according to the invention.
• ammonium salt of dithiocarbamic acid (NH 2 NCS 2 NH) which can be used in the alternative process according to the invention for the preparation of the compound (V) starting from compounds of the formula (11) is known and is also commercially available.
• the chloroacetaldehyde or chloroacetaldehyde dialkyl acetals used in the process (c) according to the invention for the preparation of compounds of the formula (I) are known and commercially available.
• formula (V) Preparation of the compounds of formula (I) are characterized by formula (V).
• the compounds of the formula (V) are the subject of the present application as new compounds. They can be produced by the above-mentioned processes (b) or (a) and (b).
• the compounds of formula (V) can exist as tautomers (see illustration above and in Example 2).
• Processes (a) to (c) according to the invention for the preparation of the compounds of the general formula (I) are preferably carried out using diluents.
• Suitable diluents for carrying out the process according to the invention are, in addition to water, above all inert organic solvents.
• aliphatic, alicyclic or aromatic optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, 2-methyl-tetrahydrofuran, methyl t-butyl ether or
• Ethylene glycol dimethyl or diethyl ether Ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or mixtures thereof with water.
• Ketones such as acetone, butanone or methyl is
• Particularly suitable diluents for carrying out process (a) are protic polar solvents such as alcohols such as methanol, ethanol, n- or i- Propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene, glycol monomethyl ether or diethylene glycol monoethyl ether in question.
• protic polar solvents such as alcohols such as methanol, ethanol, n- or i- Propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene, glycol monomethyl ether or diethylene glycol monoethyl ether in question.
• ethanol is used as the diluent.
• Particularly suitable diluents for carrying out process (b) are e.g. Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, dioxane, tetrahydrofuran, 2-methyl-tetrahydrofuran, ethylene glycol dimethyl or diethyl ether, pyridine, ethyl acetate or isopropyl acetate in question.
• Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, dioxane, tetrahydrofuran, 2-methyl-tetrahydrofuran, ethylene glycol dimethyl or diethyl ether, pyridine, ethyl acetate or isopropyl acetate in question.
• methyl tert-butyl ether is used as the diluent.
• Particularly suitable diluents for carrying out process (c) are e.g. Dioxane, acetonitrile and carboxylic acids such as e.g. Glacial acetic acid, p-toluenesulfonic acid, methanesulfonic acid or mixtures thereof.
• carboxylic acids, p-toluenesulfonic acid or methanesulfonic acid are preferably also added only in catalytic amounts.
• Suitable reaction auxiliaries for processes (a) and (b) according to the invention are the generally customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal, acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, sodium or Potassium methoxide, ethanolate, n- or i-propanolate, -n-, -i-, -s- or -t-butanolate; also basic nitrogen compounds, such as ammonia, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexy
• 0.1-20 mol% base is preferably used, particularly preferably 0.5-8 mol% base.
• reaction aids for process (c) according to the invention are e.g. Carboxylic acids, e.g. Glacial acetic acid, HC1, BF3, ⁇ SO ⁇ trifluoroacetic acid, p-toluenesulfonic acid or methanesulfonic acid, which are used directly as solvents, but can also be added to the reaction in catalytic amounts.
• Carboxylic acids e.g. Glacial acetic acid, HC1, BF3, ⁇ SO ⁇ trifluoroacetic acid, p-toluenesulfonic acid or methanesulfonic acid, which are used directly as solvents, but can also be added to the reaction in catalytic amounts.
• Preferably 0.1 to 10 mol%, particularly preferably 0.5 to 5 mol%, of the reaction aids mentioned are present.
• reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C. Preferred temperature ranges can also be found in the production examples.
• the methods according to the invention are generally carried out under normal pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - generally between 0.1 bar and 50 bar, preferably between 1 and 10 bar.
• the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess.
• process (b) according to the invention 1.5 to 3 mol of hydrogen sulfide or a salt are preferably used per mole of the compound of the formula (TV) used the same.
• the reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred at the required temperature for several hours. Working up is carried out according to customary methods (cf. the production examples).
• the rhodanide of the formula (TTT) is stirred in solvent, preferably alcohol, with a compound of the formula (II), preferably at room temperature, with a precipitate arises.
• solvent preferably alcohol
• a compound of the formula (II) preferably at room temperature
• the compound of the formula (V) in diluent preferably dioxane
• diluent preferably dioxane
• an aqueous chloroacetaldehyde solution in the presence of a catalytic amount of hydrochloric acid and boiled under protective gas.
• diluent preferably glacial acetic acid

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Thiazole And Isothizaole Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Paper (AREA)

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• 2002
  • 2002-01-15 DE DE10201238A patent/DE10201238A1/de not_active Withdrawn
• 2003
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